PHYSICAL REVIEW B VOLUME 12, 15 OCTOBER 1975 NUMBER 8 Linear methods in band theory* 0, Krogh Andersen Department of Blectrophyses, Technical Universy, Lyng. Denmark (Reeaived 14 Apri 1973) “Two approximate methods for solving the band-tructre problem in an elicient and physically transparent, way are presented and discussed in deal, The variational principe forthe one-electron Hamiltonian i used in both schemes, and the til fection ae near combination of enerayindependent augmented pane waves (APW) and muffntin orbitals (MTO), respectively. Te secular equations are therefore eigenvalue equations, near in energy. The til functions are defined with sespect toa muffintn (MT) potential and the energy ‘bands depend on the potential in the spheres tough potential parameters which deserbe the enesy ° a ° soci) p derenerss) 4 Pete eset Cee wary ‘ 215 3a bp eresyxtersaver ent eat > oe a1 noe aust ee os afr oto 3 a ous 0.23 a (lp) a7 © (ie) the one considered inSec. 1, and in the interstitial ‘rogion the potential assumes the constant value %, A. LAPW formalin For the solid we choose a set of basis funetions, named energy-independent augmented plane waves, and specified by the reeiprocal-lattice vectors 6. An energy-Independent APW is the plane wave e"'F2)¥ in the interstitial region and, inside any sphere, it is that linear combination of the fune- tions ,,(0, 7), defined in (2.2) and (2.3), which ‘matches continuously and differentiably onto the plane wave, In the sphere surrounding the atom at the origin, the energy-independent APW is there- fore HOD arr ptjuno BP | an where R=R 0G ts the sum of the Bloch veetor and a reciprocal-lattice vector, and D= D,(K*) is the log- ee Wha — Oba Oye | A El oah= wo =| = ater = (ag— OE (eM ERYF) (FY Viggg= BY +2 WR’, RIT, where R'=R+ Gand of volume, Furthermore, arithmic derivative at the MT sphere for a free electron of angular momentum ? and wave number K, as defined in (2.28). The definition (8.1) would bbe that of an ordinary APW if @(D(K"), r) were sub- stituted by (8, 7). Although the energy-indepen- dent APWs are not, individually, solutions at any ‘energy of Schrédinger’s equation in the spheres, they must, for the MT potential considered, form a complete set of functions in the neighborhood of the arbitrary energy E,.. In the conventional APW ‘method the variational freedom, arising from the overcompleteness of the plane-wave sot in the In- terstitial region, is used to remove the kink in the individual APW at the sphere. ‘This freedomisused in the linear-APW method to form, inside the sphere and for each value of angular momentum, the linear combination #(D(E), r) corresponding to the proper energy, In the representation of energy-independent APWs the Hamiltonian and overlap matrices for the MT potential may be obtained from (3.1), (2.4), and (@.6) as van Ble = 98 Vgte= Ele RF) +O" oy | Ht Blt) SE) (3.2) +. ( ) denotes an integral in the sphere while { } denotes an integral in the cell3068 iM\S=G'ss) 45° o-01s a (ght Lwwe,®, 9) ‘a8 obtained from Green’ definition wR) second identity, and the (ars adp (R’- RyUK's\las) x Bad, 498 RoR? a? (3.4) where we have dropped the subscripts 1, and where Pis the Legendre polynomial. The potential fune- tion in (8.2) is Tu’, K Bae wat cae (oe), 8.3) whore we have used (2-14) and the notation and + (OE dio" and (B') , and (B"), and WK’). ‘The interpretation of the LAPW matrix (8.2) is straightforward. For a diagonal element, the first term Is just (%y/)(K*+ Vagq~£) and, in the second term, Eww -2 ere and 0, are, respectively, te volumes of the interstitial and spherical regions. A diagonal clement of the potential function is TU B= BUC) SEES (BUDD - E) 6.) where we have used (2.31) and (2.17). From the Fequirement that the diagonal element vanishes, we then tealize that, for a single energy-Inlependent APU, the expectation valve ofthe band structire inthe extendod-zone pchome i the weighted mean ofthe contribution K+ Vay, irom the infersttial egion andthe partial entries £(,(K*)) contested by the sphere, These partial energies correspond to the boundary conditions at the sphere, defined by the free-space soitione with angular momenta I and the kinetic energy K*. The weights are, of Course, the respective probabilities for the enersy- independent APW state of belng In the inersttial region and of being in the sphere with angular mo- mentum 1, Io the approximation that the MT aphere ts mbatituted by the atom sphere of volume’ ©. KROGH ANDERSEN 2 the weights in the atomic sphere, relative to the free-electron weights W, are approximately the partial band masses uct =@K2_ aD(B) OY ON BRA nunyedie) “SED an relative tothe mass of a free electron, For the transition metal Pd, we demonstrate in Fig. 3 how its 4d mass, which is eight times that of free electrons, causes the single LAPW band to follow the 4d energy in the region of KS values where W, dominates, We may rearrange the terms of (3.2) in such a ‘way that each term becomes Hermitian, the I con- vergence is improved, and the LAPWmatrix takes the form Ihya~ eObg=(K*~ Ba+ VES) +VeRR, BD, familiar from OPW and pseudopotential theory. ‘The contribution to the pseudopotential from the interstitial region is VG ~B)= VgulGara~ THEE -F)), “while the contribution from the sphere is lve? |= v8~B|e'® -¥) (3.8) @.9) Vth B, = 00" (eel t= = 2 (eR wa VR, 1 elk, 1, @.10) where we have used (3.2). Moreover, TU, K)=(w'A= 0r'/lw=w"), (1) TU, R= wd*(K*/0*— a, (3.12) AG, K=[[e' = Bx) ~ w= ANV(w~ 0"), (13) ACK, K)= GK) (1+ (35 8/81, (8.14) with the notation Kt te, and x B. For the low values of {neoted in these expressions, the free-electron parameters D,(K*) and S6#K*) ray be obtained fom (2.30) and (2.92) or, for small values of K*, from the Laurent series around K=0, as is described in Sec, ID. ‘The potentiat functions «,(D) and (0) may then be obtained from (2.12) and (2.13) 1B. Accaraey and convergence We expect the LAPW method to yield energy bands correct to order @, as is the ease for a single sphere. This will now be proved for a constant po-2B LINEAR METHODS IN BAND THEORY 000 tential and, since this is no simpler than any other ere oy Peer peierendy CTT wwe believe the result lo be true in general, eo /} ‘We take the constant potential as the zero of en- r 1/ ergy so that V(G’ -G) vanishes. ‘The potential pa~ L 1 / rameters are now the free-electron parameters de- | a scribed in Sec. I1D and, from the relation (2.24) r 1, between (D(K*)) and 2, we realize that the leading EO} -tonrm’—ots2 (PJ). ea ‘This is of higher order than the exact term (= ©)657¢ im (8.8). We may then use perturbation theory and put ¢=2 in (3.18). ‘The diagonal element of the pseudopotential is now of order 24, while the off-diagonal elements are of order %* and, conse- quently, the LAPW energies are correct to third order while the eigenvectors are correct to first order, ‘The convergence of the sum on angular momen- FIG, 3, Expectation value of the band structure of tum in (8.10) and the strength of the pseudopotential palladium (Ref. 26) ung a single energy-Independent Eo) E00 Ks 1 ht osealng (mee) ext tog epend on the choice af energy zero in the first, APW, Atomlo sphore radius 1s 2,873 Bohr radii, Dis free-electron term of (3.8). With increasing angu- tances to the nearest reciprocal-lattice points are Indi lar momenta, the potential parameters approach cated st the bottom, Extensioa of d band is from F0) those of that constant potential which coincides with ' Fal). the true potential at the sphere and, if the zero of energy is taken at this value, the pseudopotential _ dependent APW is continuous and differentiable at components of high angular momenta will vanish as the sphere, these non-MT contributions can usually (8.15). This happens in practice when 122-3. be incorporated simply by adding their Fourier ‘Among those reciprocal-space methods that can components AV(G’-G) to (3.9). If, however, the handle transition-metal q bands, the APW method _‘*th partial band mass (3.7) differs substantially Soems to have the best G convergence, and in that from unity, we must, in addition to AV(G'~G), and case the trial function must include all plane waves together with 3, WT in (8,10), include the contribu- with a significant d contribution W, in order to re- tions involving (47q°I8V| oq) and ( jy q71S014i0q)- produce the proper angular behavior in the inter- Owing to the fast convergence of (3.10), ‘these ma- stitial region. ‘The corresponding wave numbers _trices are diagonal in [for cubie transition metals. salisty KS<6~7, when $s the atomlc-sphere radi- 3 Compaiooa wath APWsoonanen us. From the discussion of (8.6) and (8.7), this a " criterion also applies to the LAPW method (although _It was previously mentioned that an ordinary APW the eigenvectors of the two methods are not neces- 18 given by (3.1) if 6(3(K*), r) is substituted by sarily Identical to order ¢, because a plane-wave @(E, 7). Moreover, the APW matrix may be ex- ‘expansion in the interstitial region is not unique) pressed by (3.2) if, in (8.5), we perform the sub- From Fig. 8, it appears that the 25-50 energy-in- stitution dependent APW's, which for a given Bloch vector (wtB) — enl/sotBret5'~ vie) — Buc have KS=6-7, are nearly degenerate and they must era ee therefore be simultaneously included in the basis whereby the reverse transition, from the APW to set. The high values attainod by the energies be- the LAPW matrix, Is formally a substitution of yond KS=7 indicate that at this point the LAPW ma- _D(E) by its first-order expansion about B(x*). ‘trix is converged in the low-energy region, which Hence, in the LAPW method, the rapidly varying includes the d band, A complete application of the logarithmic derivative functions are substituted by LAPW method to the band structure of Cu Is pre- _linear funetions of energy, and there are no diffi- sented by Koelling and Arbman in Ref. 18. culties near the asymptotes B,,(=) of the logarith- mic derivative functions as in'the ordinary APW ‘method. For comparison with the single-LAPW re Non-MT contributions to the potential are only _sult of Fig. 3, we show in Fig. 4 the expectation important in the outer region of the MT sphere and value of the Pad band structure using a single APW. In the Interstitial region, and, since the enersy- Such single-APW bands were used In the 1953 ver~ . Nom AMT contributionsearn ©. KROGH ANDERSEN # — —= E,() 20) 1 E,(0) FG. 4. mpestaton . valu tho et sree” 3 Pd See emontona 7 1 APW. sew. E,(0) 5 KS sion of the APW method, as we shall discuss be- low. ‘This band does not have the simple appe ance of the LAPW band; it has a branch for each value of nf, and the branches are separated by the aymptotes £,,(<). The band touches the mf asymp- totes at the free-electron asymptates K*=B,(), and, even for free electrons, the single-APW band ‘will consist of individual branches sticking together a the free-electron parabola The APW pseudopotential appears from (9.8) and (8.10) when the linear function T~ cA is substituted by B(x? B)~ (D- DUK* with D=D(B). This expression is a rapidly vary- Ang fonction of energy, diverging at Ey), and this is true even for free electrons where the APW pseudopotential vanishes along K’?=2 and K®=£ only, rather than in a region of (KS, K%, B) space. At a particular energy, e.¢., the Fermi energy Ep, not coinciding with any of the asymptotes, the ABW pseudopotential is specified by the parameters D,(B,) and Vg while the LAPW pseudopotential, with 8, =, depends on the additional parameters $,(Bp). ‘These parameters only affect the bands away from the Forml energy and, if they are sat equal to zero, the LAPW pseudopotential equals to the APW psetidopotential. “This may be seen from (2.11), (@.7), and (2.8). in the 1058 version of the APW method, the basis functions are infact energy-indepenent APWs but of a more complicated nature than the ‘ones considered above. Theyare APWs of wave vector K=K+G, and with &,(r) in (3. 1) substituted by 6,(64, 7). The BF are the single-APW energies ilustrated in Fig. 4, and they are not the partial energies £,,(5,(K) that make the basis functions Aifferentiable, The basis set carries the double Index nG and, In practice, those functions corre sponding to the first few branches of EF together ‘ith all the reciprocal-lattice points used in the APW and LAPW methods must be included. Hence, the dimension of the eigenvalue problem is two or three times larger than that of the LAPW method. Moreover, the single-APW eigenvalues ZF cannot be given explicitly and their evaluation is difficult. IV. LINEARATO METHOD In this section we present a linear band-structure method in the angular momentum representation, Which is particularly sulted for closely packed structures. For the angular functions we often use the general notation Y= DL Yate» (a1) where 1 is short for Iv and Ug, 18 an arbitrary unitary matrix of dimension @Zi'1). We again con sider the periodic MT potential with one atom per primitive eell and, for convenience, we choose the atomic positions to colneide withthe lattice transla~ tions R, although in Sec. IVF we shall extend the formalism to more than one atom pet cel. A. Energyindependent MO ‘The energy-independent MTO x, (F) has a tall proportional to r""''Y,() in the interstitial region.2 ‘This part of the tail is a solution of the Laplace equation, V*y=0, rather than a solution of the Helm- holtz wave equation, (V+ E= Vqus)x=0, used for the exact MTO, andthepresent choiceleadsto im- portant simplifications of the KKR structure con stants but also to small errors, of order (E— Vu) in the computed energy bands "The energy-inde- pendent MTO is everywhere continuous and differ- gentiable. Inside its own sphere it equals @(~1~1, 5), as defined by 2.3) and (4.1), and inside any other sphere, say the one displaced by R, it is the Linear combination of the 4, (0', F- Ri)’s that mateh- es on to y,(7). Apart from the normalization, the coctficients of this linear combination are then the coefficients in the expansion about fof the 2!-pole field y"1i#¥, (7) inthe regular solutions 1F-Ri'!'y, FER) of the Laplace equation. ‘The Bloch sum of orbitals ie z ef hy @-B) (4.2) ‘has an expansion about the origin that may be writ- tenas $@)=8,61-1,7) 12) Of-1-1) “brary aaa and which is valid in the sphere at the origin. The first term is the contribution from H=6 in (4.2) and the second term is the sum of the tails coming from all other sites in the crystal, ‘The structure constants 8{., in (4. 3) form a Hermitian matrix, they may be defined by the one-center expansion Sia, 4.3) Lagan renin, 6) ‘and we shall return to them in Sec. IVD. In the basis of the Bloch sums (4.2), the contri- bution to the Hamiltonian and overlap matrices from es Ob [= BAD 0D.dbu0- (ope ey ft" oD, =o WD Dork. i sD rhe Ae duhle Doh, oy OOF Tort, LINEAR METHODS IN BAND THEORY 3071 all the spheres are just the integrals in the sphere at the origin, as given by @.4) and (2.6) in connec tion with the one-center expansion (4.3). Hence, when we neglect the contributions from the inter- stitial region, the one-center energies, stemming from the first term in (4.9), will be (27+1) degen crate and equal to E,(~~1), as given by (2.17). It will prove convenient, however, to write the one- ‘center expansion in a more general form by adding in (4.3) some constant times 6, (1, 7) to the first term and subtracting it in the tail sum. If, at the ‘same time, we renormalize the orbital, the result- ing first term may, according to @2.11), be written as :(D, ,#), where D, is an arbitrary logarithmic derivative, but different from J, and the formal one- ‘center energies become £,(D,). Hence, with the normalization pe ed=a 122 OTD 4.5) or equivalently (20s 1)ys(D,)= (C= D,)8(0,) a6) the general form of the one-center expansion 1s. 2D?) = ED $0.,7) seen Es 2 GDL) The. an ‘We have used (2.12)~(2.15) in (4.6) and we have defined a Hermitian matrix which may be written THe 1 Dy)= VES AD, MH 221+ IND, #E41/(Dg~ DB r-2 +8 x}/E9I(D,). (4-8) . Hamiltonian and overlap matrices ‘The spherical contributions to the Hamiltonian and overlap matrices in the basis of yi(D,,,#) are ot) + t, abe ot ‘as am) Th they (4.9) oy(D_) = wld (4.10)3072 ‘where the choice of D, only affects the normaliza- tion and the arrangement of the various terms. If weuse D, =-1-1, as in (4.3), Thy = Whe 1-185 4 (W910), @ and in this case the terms of order 7°, T°, and 7? in (4.9) and (4. 10) may be identified as, respective ly, one-, twor, and three-center integrals. For other chotces of D, this identification is purely formal. Before properly computing the integrals in the region between the MT sphere and the atomte poly- hedron, we mention that the simplest approximate way of including this interstitial region is to sub- stitute the atomic Wigner-Seitz sphere for the MT sphere in (4.9) and (4.10), that is, both in the structure constants (4.4) and in the potential param- ters. We thus emphasize that (4.9) and (4.10) are the important matrices of the LMTO formalism and ‘what we describe in the remainder of this section can merely be regarded as a correction to the atomle-sphere approximation (ASA). ‘The expansion (4.4) converges inside the sphere passing through the atomic positions nearest to the origin. The atomic polyhedron of any closely packec structure is included in this sphere and an integral {n the interstitial region may therefore be computed ‘entirely in the angular momentum representation from this expansion and the expansion in spherical harmonics of the interstitial step function, # which 4s unity in the interstitial region and zero elsewhere ‘This requires a double sum on L” and L’” and, in order that the accuracy be improved beyond that of the ASA, the sum must include (0", 1") $45 hence it becomes quite tedious. An Integral in the {interstitial region could also be computed entirely in the reciprocal-lattice representation by using the second factor of (3.9) for the step function to~ gether with a Fourier transform of the MTO tail, but this again requires a double summation. The most convenient way of handling the integral is, however, to evaluate the integral in the cell by'a single reciprocal-lattice sum and then to subtract the integral in the sphere by subtractions in (4.9) and (4.10). In this way, the LMTO Hamiltonian and overlap matrices become aE, = Od la Bld) = Wate BME ed @.12) 2) ERED + Vata and Of, =O xb) GELS Hab KE}, 4.19) where { } denotes an integral in the cell of yolume a ‘We want the reciprocal-lattice sum to be rapidly ©, KROGH ANDERSEN 2 convergent and to be given by 4 convenient analyt- cal expression. Moreover, (jf-1;f) should have the form of (4.10). The orbital j,(F) therefore co- Ineldes with the proper orbital in the Interstitial rregion only while, inside the spheres, it is a smooth function derived from a pseudopotential. If we let this potential be constant and equal to F,, the cor- ‘responding potential parameters are the free-elec~ tron parameters with K,=0, derived in Sec. IED and given in the first column of Table I. Conse- quently, BU, 7) = Solr) =[21+3)S"}"* (0/5) 50 that the tail of the free-electron orbital is pro- portional to r“""¥,(7), not only in the interstitial region, but also inside all other spheres, that is, B-1-1, 1/8-1-0), ossr", ‘where the normalization constant depends on the proper orbital and is given by (4.8). The recipro- cal-lattice representation of the Bloch sum is, win=uton | rs EM= ODL e* FR 4.14) where R=R 4G and Fe 21-1) (ar+9) HE Sa y, ky, 4.18) as obtained from Green's second Identity. ‘The in- togral in the cell is therefore {iE [R}= xD. IO5E exelDe) » with shee Frm) FR) 4.16) aan 1 (4.12), the difference between the two integrals in the sphere (xE+IxE)~ (3f-15) is given by (4.10) if, from 1 +(65)a*(D) in the formal one-center in= tegral, we subtract [Nol CBee) and, from 1 +(63)u(D)0() tn the formal two-cen- ter Integrals, we subtract ) w(D)- wD (4.19) and, finally, from 1+(62)%(0) in the formal three- center integrals, we subtract 0/0) (4.20) Similarly tn (4.12), the subtraction of (Vq4e~ E,) x (E-1§E) from (4.9) may be accomplished by sub-2 LINEAR METHODS IN BAND THEORY E,) times (4,18) trom w(D) in the formal one-center Integral of (4.9), by subtracting (Ware B,) times (4.19) from «(1) in the formal two-center integrals, and by subtracting (Vg times (4.20) from wit) in the formal three-center Integrals. When doing so, we have used the same Dz in xp (Dr, #) and f(D; ,F). In (4, 18)=(4. 20), we have used the subscript y=0 for the free- electron parameters and we recall that &(!)=0 and SH =21+3 ‘The above-mentioned procedure is analogous to the one followed when writing the LAPW matrix in ‘the form (8.8) and, besides its immediate purpose of including the interstitial region, it has improved the convergence of the sums on 1” in (4.9) and (4,10) because the components of high angular mo- menta are free-electron-like and hence included in the Fourier sum (4,17). In practice, the L”” sum- mations are converged when 1” <2-3, Tn (4.12) and (4.13), the two last terms, involving j, will there- fore be referred to as the combined correction term. ‘The orthonormalized wave functions are most conveniently given by one-center expansions, e.8., ) ¥@)-L L loeb -+3,. ofa, (21a) where, according to (4.7) and (2.2), the = 6ay — The /Lar(D))~ axl] (4.210) and i= (DL) ru we(DTEr-/[or(De)— wD] 20) while Al, are the LATO eigenvectors, satisfying the eigenvate equations (1,1) and the orthonormal ity conditions ELab ob aljeors. C. Accumey and the ASA ‘The energy-independent MTO is not an exact solution of Schrédinger’s equation in the atomic polyhedron; its radial part is #(-1—1, 7) rather than $(E, 7) inside the MT sphere and its kinetic energy 1s zero rather than E ~ Vay in the Inter- stitial region. We shall now investigate the induced errors whieh, for the energy bands, are of order (E~ 5) and (E~ Vqy)?AF, respectively. ‘The er~ rors of the eigenvectors are of order (E~ B,)* and B~ Vw. We first consider the effect of using (>) instead of (7) and therefore neglect the error from the interstitial rogion, i.e., we assume that Vag. or use the ASA, Since the MTO is continuous and ‘ifferentiable, the one-center expansion of the Bloch sum of exact MTO’s"™ y5(B, #) is given by (4.7) (4.214) 3073 If we choose D; = D,(E) and then substitute 4(0, #) by (8(0)/9(E)] LE, #). The condition that the linear combination Danie of exact MTOS is a solution of Schr8dinger’s equa tion at eneray E, is then that the terms proportion- alto &, (7, 2) in the one-center expansion van- ish." Prom (4.7), this leads to the set of homo- eneous, linear equations , (4.228) Eri... 48), BBN, which only have a nontrivial solution for the speci fled B and Ei DAB 5 ge aan Rt a s8f|-0, (4.220) as seen trom (4.8). ‘These are the KKR equations fr Vgie=E oF in the ASA, "” yielding the exact ener- fy B and eigenvector A.” We now consider the warlational estimates £, ard A,,,_ obtained {rom (2.1) withthe LATO Hamlitonlan and overlap ma- trices given by (4.9) and (4.10). These estimates satisty Dd |= B/D As,-0, whereas the substitution of the exact energy and ‘eigenvector into the LMTO secular equations ylelds A, ‘These equations have been obtained by choosing Dz = DAB), writing TY, as a factor of the formal tvo- and three-center integrals, and using (4. 22a) together with (2.17) and (2.23), or together with (2.24). Hence, the LMTO energies and eigenvec- tors are correct to order (E~ £,). ‘The eigenfunctions (4.21) are only correct to or- der B~ &,, a5 is expected trom the variational principle. However, since the eigenvectors of the IMTO method in the ASA are correct to third or- der, it is possible to obtain eigenfunctions of the same accuracy. Hence, from the LMTO eigenval- Ue E, and elgenvector A,,(D;), corresponding to a normalization specified by some D,’s, we sock the coefficients in the one-center expansion of the wave function correct to order (E~ 5,), From the condition of tall cancellation, expressed by (4. 22a) and (4.7), we obtain Dob la- Bhd) A, = olle- &) Danied 48,3) LX a,esojcen 28%3074 BEDI 6 oe 5 2 Tr= De ote) PEF to order (££, Inthe third line we have substi- tuted 4, by A,,(D,(Z)) which then, by the change of normalization (4.8), has been expressed in terms ot 4;,(D,). We have further used (4.6) and sub- stituted £ by £,. For the partial wave ¢,(E,, Dy ‘We may then use its Taylor series to third order In energy, and the denominator in (4.23) may, to the same order and with (2.18) and (2.25), be written (4.28) [r- DEpIME, ~ D,JOlE,) H/SONG, +428) , where ¢=£,~ E, and 6(E,) on the right-hand side should be substituted by its Taylor series to third order. If the LMTO eigenvector is normalized as {in (4.214), the wave function (4.23) will only be normalized to order F~ F, but since (%,(8)I,:(E)) zen it may easily be renormalized. We now estimate the effect on the band structure of using trial functions with improper kinetic enerey in the interstitial region. Let E= Ef and ¥=¥" be, respectively, an exact nondegenerate eigenvalie and ‘the corresponding eigenfunction of the MT Hamil- tonian H, which Is ~ 0+ Vggs In the interstitial re- gion, Correspondingly, E+d2=£/! and ¥+a¥ are the eigenvalue and normalized eigentune- ton of the MT Hamiltonian H+ 0, the center of gravity is zero for each valve of Five, 1 Ft iim Those ce Letam;imye§ dF Yap, 0) (4.31) for I>0. This follows from the invariance of the trace to unitary transformations, from (4, 25) and (4. 28a), and from Unstild’s theorem, stating that Lirail? 1 independent of f. For all canonical bands, in- cluding the § band, the first moment vanishes 1 a Wl fa bet {thiee=o, (4.32) a follows from (4.26). We have defined the ca- nonical function 81), which is “the Fermi energy on the $ acale corresponding to an occupancy of States per atom in the eanontat I band,” and the density of states tn the canonical band is au(8) 1/3400) - sa ‘The expression forthe second moment is also very simple. From (4.25), (4.26), (4.28b), the unitarity of the Wigner coefficients, and Unsild’s theorem, wwe obtain arf" sins ai f°" ainaeeatearon IN BAND THEORY son aly eles) 3 (sy ee EG (4.38) ‘hich only depends on the number of atoms in the various shells ofthe lattice and the distance be- tween the shells. For structures with several equivalent atoms per primitive cell, these rela~ tions for the first and second moments still hold, provided that Rin (4. $4) runs over the positions of all equivalent atoms measured from a particular ‘The second moment of the s=canonteal band di verges owing to the singularity at the center of the zone. The second moments of the p-canonical bands of the bec, fec, and hep (c/a = 4) structures are, respectively, 29.4, 29.2, and 28,8 which, for an idealized, rectangular shape ofthe state den- sity, correspond to the respective bandwidths (42%29.4)/#=18,6, 18.7, and 18.6. ‘The similar- ly defined canonical d band widths are 23.8, 23.5, and 23.5 for the bee, fee, and hep structures, re~ spectively. Hence, the canonical bandwidths of the three structures are essentially the same and the rmagnitudes are in close agreement with the empiri- cal Wigner-Seitz rule, which states that a band of primarily 1 character extends over the range of en- fergies where the corresponding logarithmic deriva~ live is negative. From (4.22), and with the neglect of hybridization, that is, from (4.36) below, this rule may be expressed as = 2(21+1) (147) $88,52(201) (4.38) And it yields canonical p and d bandwidths of, re- spectively, 16 and 28. As seen from (4.20), this rile is exact at the bottom of the s band, and it holds within 10% for the extrema of all the canon= ical bands in closely packed monoatomte solids that we have so far calculated. , Pure bands and hybridization We now define the pure or unhybridized energy- band structure as it is given by the ASA (4. 22) when neglecting the off-diagonal blocks of the struc ture constants. The pure n! band is therefore the nth solution of eq) BAB) HLA 2a) eT ‘where the potential function on the left-hand side, according to (2.31), increases monotonically be- ‘ween its asymptotes, and where the canonical 7 band, according to (4.34), is bounded for > 0 and is upwards bounded for 1=0. As a consequence, the relation (4. 86) between the canonteal J band and the pure ni bands are K-independent scalings, speci fed by the !-logarithmic derivative function. From the one-center expansion leading to (4.22), it may 4.36)for 0. KRoGH be realized that a pure 1 band is defined by the Property that the Bloch sum of exact MTO's h(E, #) {s the exact solution in all atomic spheres ofthe radial Schrodinger equation for the /th partial wave. ‘For the Bloch sum of energy-independent MTO's itis also convenient to use the Ii representation, and inthis ease we specify the normalteation snd arrangement of terms in the LMTO matrices by choosing D;=Di,, where phys 1-1 ~(ar+a)sh,(2eet-1)-sh,), 4.97) so that the diagonal blocks. of 4 11 (4.8) van- ish. ‘The Bloch sum y(Dt, 7) only has one angu- lar momentom component ofthe same f, namely, (Dh, 9), in ts one-center expansion (6.7), and the corresponding formal one-center energy is the variational estimate £y(0f) (2.17) ofthe pure »! energy band given implicitly in (4.38). From @12, w,(D},)=0\(-1-1) +ESOH-1-1)8}/0-8}), (4.38) where “ser ey MN) __ase* ) arayse) “wei-1)-wH + 9% and the alternative expressions follow from (2.18). We may define the energies C,, and V,, a8 those where the [-logarithmic derivative funetion takes the values -1=1 and {, respectively. For free electrons, these energies were specifically con- sidered in Sec. IID and since Va) =0 we name Vs, =£,(0) the square-well pseudopotential. From (4,31) and (4.386) we name Cj, =B,(-1~1) the cen- ter of the band. We further define the intrinsic band masses es LES 7080) 2-28" (G)=- 1S 4By(~ 1-1) [Cop ot(-7- yt THe) (4.40) sister lt and raf [1/2r+ ay) S*6t(v,0F* (4.41) which, from the values of the free-electron prob- ability density 4f given in See. ITD, are seen to SSS oi y-o SDN) = ai Jove esul » Oe [[olDi) -w0,), [lei ANDERSEN a equal, respectively, u(-/~1) and u(t), as defined in (8.7). If we then put B, =C, in (2.17) and (4.38), we may state that the pure vl energy-band struc ture is derived from the canonical I band structure by fixing the band position through C,;, scaling it by usi8%, and distorting it nonlinearly by @)(~!~1)/ #,(0) and (6,). ‘The potential parameters for hep. ‘transition metals may be found in Tables I and IT of Paper Il, and those for free electrons were given in Table I.’ For a given J, the values of the dis- tortion parameters (— 1 1)/0(0) ana (62) vary little among similar atoms provided that the D,'s are similar and, using typical values, we find from (4,85) and (4.38) that the width of the pure band is, of order 10S8%(-1~1). For transition-metal d bands (- 3)/#(2) is numerically far less than unity, the distortion is therefore small and the d band ex tends approximately from 7.5S%(- 3) below to '598%(— 8) above the band center. For the bottom of the s band, we find from (4.25), (4.27), and (4,29) that sf,~ — 61S)", and with Ey =V., (4.38), (4.39), and (4.41), reklay y (4.42) as expected. The pure bands for hep free electrons are shown in the second pane! of Fig. 6. ‘The hybridization matrix in the 1 representation is (48). 1) T=1ak 4 bEBS) (1-1) I=748he Fe sD = She > a8) which vanishes for !"=!, ‘The Hamiltonian and over- lap matrices in the ASA, (4.9) and (4.10), only have contributions to their diagonal elements (P and’ =1) from the formal one- and three-center Integrals. The one-center integrals yield the pure- band F,(Df,), which only depends on the potential parameters of the same /, while the three-center integrals, with reference to (4.22), may be re- gardod as the second-order contributton from the partial waves of other angular momenta. ‘The single-LMTO estimate (x41 1x8 )/(xhulaka) 1s therefore different from, and more accurate than, the pure-band estimate but it depends on the poten tial parameters of all angular momenta, We named Tyr; the hybridization matsix be- cause the secular equation in the ASA (4.22) may be written as (4.44)12 LINEAR METHODS IN BAND THEORY ‘where the simple eigenvalue equation (4.44) is valid ‘when £=Ey(D}.)=£," (Df), and when we neglect (hye) and'(68,), that is, when £, is chosen near the assumed crossover of the two pure bands. Un- der the same conditions, ¥ yy, equals the formal two-center contribution to the LMTO hybridization matrix (f+ «1H ~ Bhi). ‘The hybridization between the s band and a d band of negligible distortion #(-8)/#(2) is, ac~ cording to (4.43) and (4.6), described by ‘ M8) ge =i Tha lo WDB - 00) Og) Per BFE for k= 0. ‘The limiting value ts identical with the ‘result of Hoine’ when the mass at the bottom of the 5 band is unity, and it has been obtained here by noglecting the parameters (3) and using (4. 28) for Shas under the aseumption that the constant term vanishes as is the ease in cubie exystal. ‘As mentioned in connection with (4.28), the ca~ nonieal and the pure p band have a branch which is discontinuous at the center of the zone (this is the second 7; band in Fig. 6), and the energy band only becomes continuous through hybridization with the s band. In cubic structures the p level at the genter of the zone F is triply degenerate, and when Eapproaches P along the # (001}alrection, the ca~ nonieal doubly degenerate 4, band Sf, 3:14 gS con tinuously to the value 6 but the canonical a, band shyio tends to ~12. The A, band does not hybridize with the s band while the sP hybridization constant for the 4, bands tends to ~675(kS)"!. For small nonzero # values, (4.22) now ylelds [+4 Gs)*5,2)][5,(8)+12]=18,, where 8(B)# 221+ 1)[D,(e)+1+1/[D,\@)-0)« Consequently, the P-like solution tends to 18-12 ————— Hienl®) = pan(—1 = 1, F-G)Og ‘The Hermitian, canonical structure matrix is then where Sis the average radius, defined by the con- dition that (4x/3)S "i=. ‘The coefficients g were defined in (4. 27) and the lattice sums, periodic in Y-Q, are 3 ay, (al sR det (SP waver @r 440) Pe repelll FAB) Sb yl-1=V) of AD Sere F-O) eagett % ae stten ® Se /SI 885, /9)81 rari me ® OO 2h, 3079 =6 and is therefore continuous at T, regardless of the 6 potential parameters. The 6-like solution ray still be written in the form of (4.42), but with the mass substituted by t9=1e/ DAV =TL=¥ Vp) + (4.48) where ¥,=(V,—V_S* ‘This expression is in ac~ cord with a result of Bardeen.” The hybridized hep free-electron energy bands in the ASA are shown In the third panel of Fig. 8. F, Several atoms per primitive cell, ‘We shall briefly indteate how the LATO formal- ism is moeified when the primitive cell contains fespheres, centered at positions =G, with asso- ciated potentials r(|F—Q1). Groups of identical ‘Moms at equivalent positions are labeled by f while the fy atoms within & group are labeled by @. Tn the ease of compounds, there is little justification for using a common interstitial potential Vays and inthat ease we circumvent the MT construction by using the ASA with judiciously chosen sphere radi Sc. Subject to the condition thatthe sum of the sphere volumes equals that ofthe primitive cel, the spheres shovld according to (4 24) have litte ‘overlap and, in the region of overlap, the Kinetic nergy should be small. ‘The radit specify the re- gions in which the self-consistently obtained charge density willbe spherically symmetric and, subject to the restrictions set by the ASA, they should therefore in principle be chosen s0 as to minimize the total energy of the ground state. Ts analogy with (4.2) and (4.8), the Bloch sum of MTO's in the flam representation is 5 whe -Z KyaunlF-R-O) , (4.48) and is expansion nthe sphere at #18 WS ere) (4.47) —————————————— with 3=R-3. m (4,14) and (4.17), the Fourier transform of the pseudo-MTO is given by Firen(R)= (2141) (2143) (49S 3/9) [isa KS )/KS) Wm 0" a, (4.49) ‘With the following definitions and substitutions,3080 the remainder of the LMTO formalism in the pre~ ‘vious sections can be taken over directly. If we define the radial funetions ®,,(7) and 4,(7) such that they vanish for 7>S,, we may use the follow- {ing generalization of (2.8) and (4.1): 03D eu(lF- Sper QDihiens 2 + (4.50) and analogously for 6,(). Here Lis short for flu 2d Upey is an arbitrary Unitary matrix of dlmen- sion (2l+1)h,. ‘The bracket (| | ) now indicates the fim of integrals in all spheres of the cell and, con quently, (y+) and (y-141%,) vanish wen tL, The potential parameters ony depend ot and Vand f! should therefore be substituted for T nd qm for m. ‘The # eaponteal bands 8, are the (2th, eigenvalues of hye aryanee Self-consistent calculations ase almost impera- tive for compounds and for this purpose the ASA 18 extremely efficient. "The spherically symmetrized density of band electrons ina aphere of type f may be expressed as asosoy=h a7 \oht|¢ CY" xweye.nae, — 4.50 sere the origin is taken at one ofthe G's and where, upon Taylor expansion of (5,7), the in- togral over energy redueos to 2 um involving the energy motnente, ‘The number of states in a ephere of type f with angelar momentm J, and with ene trgies inthe interval (15 "a) eS san Es (4.52) whore, according to (4.28), a= OH ai.) and aio (D lage)" With this atomie-sphere representation of the charge density, the Coulomb potential may easily be found by solution of the radial Poisson equation {in each sphere and by calculation of the Madelung shifts employing the 5-structure constants. en] ( Sera MBN oa sult m) (tems ah! ©, KROGH ANDERSEN V. RELATIVISTIC EFFECTS In accurate energy-band calculations relativistic effects can only justifiably be neglected for materi- als of atomic number less than about twenty. The relativistic shift of the 4s band with respect to the 8d band is ~12 mRy in Ti (Z=22), and the 3d spin~ orbit coupling parameter equals 1.5 mRy."* For Tu (Z=44), the corresponding energies are, re~ spectively, ~70 and 10 mRy and, for Os (Z= 76), they are ~ 280 and 35 my. This separation of the relativistic effects into mass-velocity and Darwin shifts, which may be taken into account merely by ‘changing the potential parameters, and the effect, of spin-orbit coupling, which alters the symmetry of the Hamiltonian, is not only possible but it is. also extremely convenient, because the spin-orbit ‘coupling parameters f, are smaller than the rela~ tivistic shifts by typically one order of magnitude. Moreover, only in small regions of & space, near certain polnts of degeneracy, is the spin-orbit splitting as large as (1+4)f, and even this energy is considerably smaller than the width of the ! band. ‘We shall then, for the purpose of conceptual sim- plicity and with little or no loss of accuracy, in- clude the relativistic effects in the LAPW and LMTO methods by formally using the Pauli Hamil- tonian®® vievcet(e- ose" 3%) +a-T inside the spheres, and treating the spin-orbit cou- pling term as a perturbation. A. Relativistic formalism fo single sphere ‘The entire formalism of the previous sections applies for the Paull Hamiltonian without the spin- orbit coupling term, provided that the radial wave functions, and hence the potential parameters, are obtained from radial equations which include the mass-velocity and Darwin terms ~ ¢"[(E =») +0"ld/ar)). ‘The trial function ®4_(D, #) is now (2.5) times one of the spin functions, + or +, and the spin-orbit coupling matrix, to be added to (2.4), 1s (Seq DY] 3B T| Bq (D)) = E47, D) tm’ | Em). Here, Ontemen (tm) Um + 1) 6.0) Byam)2 LINEAR METHODS IN BAND THEORY and the dependence of the radial integral £,(D’, D) ',(D")|§1,(D)) on the logarithmic derivatives may be accounted for as follows. ‘The energy de- rivative function at £, of a radial wave function ‘which is not normalized to unity in the sphere, e.g.,, IE)OLE, r), 18 a Linear combination of 64(7) and $,(r) and it may therefore be written as a con- stant times one of the functions #(7) in (2.2). wwe choose 1()6(B, 7) to be the solution which re- sults from integrations of the radial equation when ‘the initial condition at 7 =0 is independent of ener~ gy, the corresponding energy derivative function ‘®(D!, r) vanishes (as r'*#) near the nucleus where the relativistic operators are effective. We may then assume that £(r)#(D!, r) vanishes everywhere {in the sphere and, {rom the equation obtained from (2,11) when substituting ! by D, and -!~1 by Dt, ‘ WDD 5 yx 2) gupt 90,0)» (1-SBh) esr SB 8047), ‘we obtain 1 aye (x22) (y 2) etry, »)= (1-22) (1-22) 6, sn terms ofthe two new potential parameters, 6, @rlE1G,) and D!. Since I(E)p(E, ) have the hormatization usally obtained in tameriea!inte- trations of the radial equation, the parameter Di Io most easily tained by differentiation of the amplitude at the sphere and using (2.9), i.e., 2) 1 a8 Beir 8 Fag (6.9) For a given boundary condition D, angular quan- tum number /, and radial quantum number », the ‘Paull Hamiltonian then has an (J+ 1)-fold degenerate solution of energy £(D) +$1§(D) and an I-fold degen- erate solution of energy (D)—3(I+1)£(D), where E(D) is given by (2.17) and where the spin-orbit, coupling parameter is (0, D) THD * ‘The corresponding exact energies Byaia(D) and E,u(D) of the Dirac Hamiltonian are te inverse | ) 6.4) oat functions of the Dirac logarithmic derivative fune~ tions 2° 5) py vg SB PAB) “8 ig) *~K~V*S Fy and, since the radial Dirac equations are compu~ tationally quite simple, we shall now indicate how the potential parameters may be obtained from the solutions /,(£, 7) and g4(F, r) of these. As usual, ‘is the combined quantum number for 2, j, and 4. With the normalization Site, eettesrtaren, and provided that the kinetic energy in the outer re- gion of the sphere is much less than c= (2x137)* Ry, the representation in Sec. IK of the logarithmic de- rivative functions is valid when g(B) 1s substituted for O(E), and x is substituted for J. With the cholee of logarithmic derivative Dyr=Dyorter=Doyet + the potential parameters may then be obtained from the Dirac parameters as rae, (t+ 1)6%,= +a, I+) Ody = C+ V8, rd, ts 1)e8.B.= 0+ Det, ane, and Boater Mabon Bret» oD) = (21+ 1b 8 Meds ~28, ‘The approximation of attributing the D dependence of the splitting Fy,--1(D)~Ey,(D) between the Dirac logarithmic derivative functions to the nor- malization effect described by (5.2)~(5.4) can be justified by comparing the value «(D!), obtained from (5.5), with the mean value [0+ 1)0.p (4) +o, (DPY/(2l +1) obtained from (5.9) with @ substituted by g3 for the 6p parameter of Pt (Z=78), both values are 5.8 Ry and, for the d parameter, both values are ~ 1,58 Ry. B, Spinorbit coupling in LAPW method ‘The energy-independent APW is given by (8.1) times one of the spin functions, + or ¢, and the spin-orbit ‘coupling matrix to be added to (8..2) or (8.8) is therefore ype BT ho as a iy where P! Is the derivative of a Legendre polynomial. (2141) E(B", B)/S848 = Dey 1B) ~ Deel) ky) SL revere. Mjurs) jes) BB) se? With the substitution (6.8)3082 ©. KROGH ANDERSEN 12 the matrix (5.6) equals a term of the ordinary, relativistic APW method. ‘The Bloch sum of energy-independent MTOs is given by (4.2), or its generalization approximate for sev- eral atoms per primitive cell, times one of the spin functions, # oF + ‘The spin-orbit coupling matrix to be added to the Hamiltonian matrix (4. 9) or (4.12), is therefore Gb /e8-Tb te, DOU! [2)- (Dut ES py lege belt) > In the Hlgm representation rteqm? | team) =04 iredell?m Om) , Le) Th re 6.7) so that the sums on ” in the Second and third terms of (5.7) reduce to single terms. In the ili represen- tation eons a eeBitn day om! |x Lomxst 0 that the sums on Z"”" are sums over the canon- seal band index i ‘The common approximation of retaining the spin- orbit coupling in the one-center integral only, amounts to neglecting the variation of the coupling parameter £ across the band, i.e., its D depen- dence. This may be seen from (5.') when choosing D,=~1-1, in which case the first term of (5.7) is the true one-center integral. If, on the other hand, wwe choose D, = Di,, and use the ili representation, it is not a bad approximation to neglect in (6.7) all other terms but the first. VL. CONCLUSION In this paper we have presented the details of the linear-APW and -MTO formalisms and investigated their respective merits. Of the two methods, the LAPW method is the most generally applicable, its accuracy is arbitrary in the sense that F, is arbi- trary, and {¢ may be used at high energies and for open structures because the plane-wave set isover~ complete in the interstitial region so that non-MT. contributions to the potential may be included. Since the plane-wave part of the energy-independent ‘APW is continued smoothly inside the spheres, the hnon-MT contributions enter primarily through’ thelr Fourier components. When d bands are present, L [ue myd+meneexne Liem v-meeexee -Limxay , ——— the angular behavior in the interstitial region cannot be represented by less than 25-50 plane waves per atom and, if applicable, the LMTO method is far sore efficient. Tu this case, only the nine s, p, and d MTOs are needed per atom but, since the method has additional errors, proportional to UE — Vai), it only useful for closely packed structures atd low energies. This method is com- Putationally very fast, and it may be simplified ‘through the atomic-sphere approximation and fur~ ther, through the neglect of hybridization, in which case there are no matrix diagonalizations to be per~ formed; the energy bands are just the canonical bands sealed nomniformly by the potential param- eters. A theory of the electronic structure of hep transition metals, based on the LMTO method at its various levels of simplicity, ts presented in the following paper. ACKNOWLEDGMENTS I wish to express my gratitude to Professor ‘A. R. Mackintosh for his interest, help and en- couragement at all stages of the present work. Dr. O. Jepsen made the linear-MTO method work {in practice, and performed the computations illus~ trated in Figs. 9 and 6. I have benefitted greatly from many fruitful discussions with him. Useful comments from Dr. D. G. Pettifor, Dr. N. Egede Christensen, Dr. H. Skriver, and Dr. G. Arbman are also gratefully acknowledged.2 LINEAR METHODS *Work supported in prt bythe AEK Research Establish rent, isd. 40, Jepsen, 0. K, Andersen, and A, R. Mackintosh, following paper, Phys. Rev- Bz, max (VTS). 4p, Hohonborg and W. Kohn, Physe Rev. 196, B86 Gott); Le Hedin and B. L, Lundgelst, J. Phys. C &, 2006 (9TH), U. von Barth and di, iid. 5, 1029 {1972}; 0. Gunearsson, 3. Phys. F to be peblished); J.C, Slater, Quantum Picory of Molecules and Solids ‘btectaw-til, New York, 1974), Vo. IV. 9p, W. Averill, Phys, Rov. B 4, 3915 97H), Ts a, Yiatox, 4. B. Conldin, ty de C, Slater, and 3. 5 Triokey, J. Phys, Chem, Solids 4, 162% (979), G. ‘Aviman and U, von Barty J, Pagss F 5, 1159 0975), Ve, Nori, A. R, Willams, and J.P, Jana, Phys, Rev. 8 3, S310 (974); Jo Fs danaky A, R. Wil ame, and W. L, Moruzsi, id. 6, 4907 W972) 11, 1522 910). Contrary tothe conlusion reached ty ‘ina ef af. Srom their sonrelaivistc eaeslations, we bollve that te flest-prnciples potential of Hedin and {Lunagust (Ref. 2) describes the Fermi surface of Cu exceedingly well, The reason is at th Diras potoaial parameters (Sec, V) obtained from Chodoron’s potential Show thatthe relativistic smd band sift approximately 20 may, whichis three times larger than estimated by Jana ota 45, Madsen, 0, Jepsen, and 0. K, Andersen (mpub~ ished). ‘Seo, fF instance, T. Ls Loucks, Augmexled Plane Wave ‘Method (Benjamin, New York, 1897}, J. 0. Dimmock, Sottd Sate Physiea (Academic, Now York, 1971), Vol- 2. ‘Sec, for instance, Bs Segall and F 5, Ham, Methods ‘n Computational Physies (Academic, New York, 1908), Vol. 8, Chap. 7. 1U. Mi. Ziman, Proc. Phys. Soe. Lond. 86, S97 (900); 4, Hubbard, tid. 92, 921 (967); V Heine, Phys. Rov. 13, 075 Ui00. For a review, see, N. W. Dalton, Computational itethods in Band Theory (Plenty New York, 197). p. G. Potion, J. Phys. © 5, 97 972). 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D, Koellieg and G, 0, Axbman, J, Paya, F (to be published, 0, epson and O. K. Andersen (anpublished), 2, Jariborg and G. 0. Arbman (unpublished). HB! VU. Condon and G, iM, Shortley, The Theory of Atomic Spectra (Cambridge U.P., Cambridge, Eagland, 4051), By, M, Salfren and J. ©, Slater, Phys, Rev, 92, 1126 4953), Spor a roviow seo L, P, Mattholss, J, H, Wood, and A. C, Switendick, in Methods in Computational Phystes ‘eademie, New York, 1968), Vol. 8, and references ‘contained therein, HO, Jepsen, Phys, Rev. B12, xox (975). gi, i, Rose, Relativistic Electron Theory (Wiley, Now Yor, 1961), Mo, K, Andersen, Phys, Rev. B 2, 888 (1970).